US4511601A - Copper metallization for dielectric materials - Google Patents

Copper metallization for dielectric materials Download PDF

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Publication number
US4511601A
US4511601A US06/494,475 US49447583A US4511601A US 4511601 A US4511601 A US 4511601A US 49447583 A US49447583 A US 49447583A US 4511601 A US4511601 A US 4511601A
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United States
Prior art keywords
firing
glass frit
copper
copper oxide
paste
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Expired - Lifetime
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US06/494,475
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English (en)
Inventor
James R. Akse
Stanley A. Long
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Philips North America LLC
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North American Philips Corp
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Priority to US06/494,475 priority Critical patent/US4511601A/en
Assigned to NORTH AMERICAN PHILIPS CORPORATION 100 E. 42ND ST, NEW YORK, NY 10017 A CORP.OF DE reassignment NORTH AMERICAN PHILIPS CORPORATION 100 E. 42ND ST, NEW YORK, NY 10017 A CORP.OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: AKSE, JAMES R., LONG, STANLEY A.
Priority to EP84200668A priority patent/EP0125730B1/en
Priority to DE8484200668T priority patent/DE3475799D1/de
Priority to JP59096309A priority patent/JPS59226178A/ja
Application granted granted Critical
Publication of US4511601A publication Critical patent/US4511601A/en
Priority to HK659/90A priority patent/HK65990A/xx
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5127—Cu, e.g. Cu-CuO eutectic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5183—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks

Definitions

  • the invention relates to a method of providing a copper metallization on a dielectric or semiconductive body.
  • the invention also relates to a method of providing a copper metallization on a base metal electrode multilayer capacitor.
  • the invention further relates to a metallized dielectric or semiconductive body.
  • Dielectric and semiconductive materials have many uses, particularly as electronic components.
  • dielectric ceramics having a perovskite structure make very good capacitors.
  • Barium titanate and calcium zirconate ceramics are typically used for such purposes.
  • Other oxides may also be used.
  • Electrodes In electronic components made of dielectric or semiconductive materials, electrical connections to the components must be provided. These are typically provided in the form of metal electrodes, or metallizations, which are attached to the component body. Noble metals such as silver and palladium and alloys thereof make excellent electrodes due to their excellent electrical conductivities and due to their resistance to chemical oxidation. However, such electrodes are very expensive.
  • base metals may be used for metallizations on components.
  • conductive films made partially of nickel, cobalt, and copper have been made in the past. (See, e.g. U.S. Pat. No. 4,122,232.)
  • Some of the considerations affecting the use of such base metal metallizations include their susceptibility to oxidation and the strength of the bond attaching the metallization to the dielectric.
  • additional problems include the difficulty and expense of obtaining an easily dispersible copper powder (that is, the difficulty and expense of attaching a molecule to the copper particle which will interact properly with the solvent system), and the maleability of the copper which makes it difficult to grind the copper into a powder form while controlling particle size, agglomeration and surface area.
  • Treptow discloses a method of providing a copper metallization on a refractory substrate. First, a mixture of copper or copper oxide and reduction-resistant glass frit is suspended in a volatile medium to form a dispersion. This mixture is applied to a substrate, and the coated substrate is then fired in an oxidizing atmosphere to form a bond between the substrate, glass, and copper oxide. After oxidation, the coated substrate is fired in an atmosphere reducing to the copper oxide, so as to reduce the copper oxide to copper metal.
  • the glass frit appears to create strains at the metallization-substrate interface due to (i) the creation of reaction zones where the glass frit tends to react with the ceramic body, and (ii) a mismatch between the thermal coefficients of the glass, the glass-substrate reaction zone, and the substrate.
  • These strains sometimes result in cracks in the dielectric upon thermal cycling.
  • the glass frit is vulnerable to chemical attack which may occur during subsequent processing of the component. For example, if the metallized component is electroplated to provide a solderable terminal, the electroplating may chemically attack the glass frit in the metallization.
  • a method of providing a copper metallization on a dielectric or semiconductive body consists essentially of the steps of mixing copper oxide powder and up to 15 weight percent reduction-resistant glass frit, dispersing the mixture in an organic vehicle and a solvent to produce a paste, and applying the paste to the body to provide a coating thereon. This is followed by drying the coating to remove the solvent, firing the coated body in an oxygen atmosphere at a temperature below the melting temperature of the glass frit to remove all or part of the organic vehicle, and firing the coated body a second time in an atmosphere which is reducing to the copper oxide. The second firing is at a temperature from 700° to 1050° C. for from 120 to 5 minutes. The second firing is effective to convert the copper oxide to copper metal.
  • a method of providing a copper metallization on a dielectric or semiconductive body consists essentially of the steps of providing a copper oxide powder with no glass frit, dispersing the copper oxide powder in an organic vehicle and a solvent to produce a paste, and applying the paste to the body to provide a coating thereon. This is followed by drying the coating to remove the solvent, firing the coated body in an oxidizing atmosphere to remove all or part of the organic vehicle, and firing the coated body a second time in an atmosphere which is reducing to the copper oxide. The second firing is at a temperature from 700° to 1050° C. for from 120 to 15 minutes, so as to convert the copper oxide to copper metal.
  • a method of providing a copper metallization on a base metal electrode multilayer capacitor consists essentially of the steps of mixing copper oxide powder and 0 to 15 weight percent reduction-resistant glass frit, dispersing the mixture in an organic vehicle and a solvent to produce a paste, and applying the paste to the multilayer capacitor, to provide a coating thereon. This is followed by drying the coating to remove the solvent, firing the coated multilayer capacitor in an oxidizing atmosphere at a temperature below the melting temperature of the glass frit to remove all or part of the organic vehicle, and firing the coated multilayer capacitor a second time in an atmosphere which is reducing to the copper oxide. The second firing is at a temperature from 700° to 1050° C. for from 120 to 15 minutes. The second firing is effective to convert the copper oxide to copper metal.
  • a metallized body comprises a reduction-resistant dielectric body and a metallization consisting essentially of copper.
  • the metallized body is preferrably a ceramic having a perovskite structure.
  • a ceramic may comprise, for example, barium titanate, calcium zirconate, strontium titanate, or strontium zirconate.
  • the organic vehicle is preferrably removed from the coated body by firing at a temperature of from 200° to 450° C. in air.
  • the second firing step is preferrably performed in a reducing atmosphere having a partial oxygen pressure less than 9.5 ⁇ 10 -6 atmospheres.
  • the reduction-resistant glass frit consists essentially of oxides of (i) barium, boron, and aluminum, (ii) sodium, boron, and silicon, or (iii) lead, boron, and silicon.
  • the second firing is in an atmosphere which is substantially nonreducing to the glass frit, at least for the duration of the second firing.
  • the invention is advantageous because the copper oxide-based paste is easily dispersed with conventional dispersing agents. Moreover, the physical properties of the copper oxide powder can be easily manipulated by conventional milling techniques. Finally, the inventive method produces a copper metallization with fewer steps and, in one embodiment, with no glass frit.
  • FIG. 1 is a cross-sectional view of a metallized multilayer capacitor according to the invention.
  • Copper metallizations according to the present invention are manufactured in the following manner. Copper oxide (cuprous or cupric) powder is mixed with a reduction-resistant glass frit. Preferrably, both the powder and the frit are ground to subsieve minus 325.
  • the reduction-resistant glass frit comprises 0-15 weight percent of the mixture.
  • reduction-resistant glass frit (defined further below) means both reduction-resistant and nonreducible glass frit.
  • the copper oxide and glass frit are dispersed (with a dispersing agent such as Duomeen CTM in kerosene) in an organic vehicle to form a paste.
  • a dispersing agent such as Duomeen CTM in kerosene
  • organic vehicles are available, for example ethyl cellulose in terpinol or cellusolve acetate.
  • the viscosity of the paste may be adjusted with a solvent to achieve the consistency needed for applying the paste to a dielectric body. Suitable solvents include cellusolve acetate and butyl cellusolve acetate.
  • the next step in the process is applying the paste to the dielectric or semiconductive body to form a coating on the body.
  • the paste is applied by dipping, but it may alternatively be applied by screen printing.
  • the viscosity of the paste is an important process parameter for obtaining high quality metallizations.
  • the dielectric or semiconductive body on which the paste is applied may be many materials.
  • the body may be an oxidic ceramic having a perovskite structure.
  • This class of materials which includes barium titanate and calcium zirconate, is known for materials having large dielectric constants. These materials are useful, for example, in the manufacture of ceramic capacitors.
  • the dielectric or semiconductive body After the dielectric or semiconductive body is coated, it is allowed to dry to remove the solvent from the paste. Thereafter, the coated body is fired in an oxidizing atmosphere to remove all or part of the organic vehicle, leaving only the copper oxide and glass frit (if any) remaining.
  • the firing temperature in this step is below the melting or softening temperature of the glass frit.
  • the firing temperature is from 200° to 450° C. and the firing is in air.
  • the coated body is fired a second time, this time in an atmosphere which is reducing to the copper oxide.
  • the second firing is at a temperature from 700° to 1050° C. for from 120 to 15 minutes (the higher the firing temperature, the shorter the firing time), and is in an atmosphere which is substantially nonreducing to the glass frit (if any) at least for the duration of the second firing.
  • the partial oxygen pressure of the firing atmosphere is preferrably less than 9.5 ⁇ 10 -6 atmospheres depending on the firing temperature.
  • the copper metallization is formed by reducing the copper oxide to copper metal.
  • a bond, affixing the copper metallization to the dielectric or semiconductive body is formed. This bond is formed with or without the presence of glass frit. While the bond appears to be stronger with glass frit, the body appears less susceptible to cracking when provided with a fritless metallization.
  • a noteworthy feature of the method according to the invention is the discovery that in the fritted metallization it is not necessary to provide an additional firing step (between the organic vehicle removal and the final reduction firing) at a temperature above the melting temperature of the glass frit to commence formation of a bond between the substrate, glass, and copper oxide.
  • the firing atmosphere is reducing to the copper oxide but preferrably not to the glass frit, if any frit is used.
  • This requirement functionally defines the reduction-resistant glass frit. That is, a reduction-resistant glass frit is one which can withstand firing in an atmosphere which is reducing to the copper oxide used.
  • Such glass frits (oxides of various elements) will either (i) reach equilibrium with their elemental constituent at very low concentrations of the pure elements, or (ii) proceed toward equilibrium with their pure elements very slowly in comparison to the firing time in the reducing atmosphere so that only a small conversion from oxide to pure element takes place, or both (i) and (ii) will hold true.
  • Suitable glass frits for use in the invention include nonreducible BaO-B 2 O 3 -Al 2 O 3 systems such as 5-65 weight percent BaO, 0-35 weight percent Al 2 O 3 , and 25-85 weight percent B 2 O 3 , with up to 5 weight percent Na 2 O or K 2 O substituted for BaO, up to 15 weight percent MgO, CaO, or SrO substituted for BaO, up to 50 weight percent SiO 2 substituted for B 2 O 3 , and up to 5 weight percent ZnO, NiO or CuO substituted for BaO.
  • a preferred glass frit in this system consists essentially of 60 weight percent BaO, 33.5 weight percent B 2 O 3 , 5 weight percent Al 2 O 3 , and 1.5 weight percent Na 2 O.
  • Na 2 O-B 2 O 3 -SiO 2 system such as 25-55 weight percent B 2 O 3 , 0-10 weight percent Na 2 O, and 35-75 weight percent SiO 2 , with up to 5 weight percent K 2 O substituted for Na 2 O.
  • a preferred frit in this system consists essentially of 38.3 weight percent B 2 O 3 , 7.7 weight percent Na 2 O, and 54 weight percent SiO 2 .
  • a reduction-resistant glass system suitable for use in the invention is the PbO-B 2 O 3 -SiO 2 system including glasses such as 50-80 weight percent PbO, 15-25 weight percent SiO 2 -15 weight percent B 2 O 3 , 0-5 weight percent Al 2 O 3 , 0-5 weight percent Na 2 O, and 0-4 weight percent TiO 2 .
  • a preferred composition within the system consists essentially of 63 weight percent PbO, 15.4. weight percent SiO 2 , 15 weight percent B 2 O 3 , 0-6 weight percent Al 2 O 3 , 2 weight percent Na 2 O, and 4 weight percent TiO 2 .
  • FIG. 1 shows a cross-section through such a device.
  • the base metal electrode capacitor depicted in FIG. 1 is made up of layers 10 of a dielectric or semiconductive material separated by layers 12 and 14 of base metal electrodes.
  • the structure is built up by stacking layers of electroded green ceramics and then firing the layered structure at a high temperature to densify the ceramic. So as not to oxidize the base metal electrodes, the structure is fired in a reducing atmosphere. Consequently, the dielectric must be a reduction-resistant ceramic.
  • the electrodes 12 and 14 do not extend completely across the dielectric layers 10. Each electrode 12 extends to one side of the ceramic (the left side of FIG. 1), while each alternate electrode 14 extends to the other side of the dielectric (the right side of FIG. 1). All of the electrodes 12 can be electrically connected together, and at the same time all the electrodes 14 can be electrically connected together to form a network of capacitors electrically connected in parallel. These connections are accomplished with metallizations 16 and 18 according to the invention. The device so constructed can now be provided with leads (not shown) soldered onto metallizations 16 and 18.
  • Table 1 shows several examples of dielectric bodies provided with copper metallizations according to the invention. Also shown in Table 1 are comparative examples not made according to the invention.
  • the dielectric body was a modified barium titanate.
  • the electrode paste was applied by doctor-blading a thin layer of paste onto a substrate, and then dipping the dielectric body into the layer of paste. Except as noted, the coated dielectric body was fired to burn off the organic vehicle and was then fired at a peak temperature of 940° C. for 5 minutes.
  • the atmosphere of the second firing is given in Table 1.
  • the pull test whose results are reported in Table 1, was an axial pull test.
  • the number reported in the Table is the force in pounds recorded at separation of the metallization from the substrate.
  • the solderability reported in Table 1 is a subjective evaluation, based on observations that in each case the entire termination was easily wettable by 60-40 (tin-lead) solder, with no appreciable bare spots.
  • Table 1 illustrates that the copper metal-based paste does not form as strong a bond as the copper oxide-based pastes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
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  • Ceramic Capacitors (AREA)
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US06/494,475 1983-05-13 1983-05-13 Copper metallization for dielectric materials Expired - Lifetime US4511601A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US06/494,475 US4511601A (en) 1983-05-13 1983-05-13 Copper metallization for dielectric materials
EP84200668A EP0125730B1 (en) 1983-05-13 1984-05-10 Copper metallization for dielectric materials
DE8484200668T DE3475799D1 (en) 1983-05-13 1984-05-10 Copper metallization for dielectric materials
JP59096309A JPS59226178A (ja) 1983-05-13 1984-05-14 銅金属被覆の形成方法
HK659/90A HK65990A (en) 1983-05-13 1990-08-23 Copper metallization for dielectric materials

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EP (1) EP0125730B1 (enrdf_load_html_response)
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US4619836A (en) * 1985-12-31 1986-10-28 Rca Corporation Method of fabricating thick film electrical components
US4799127A (en) * 1986-07-29 1989-01-17 Tdk Corporation Semiconductive ceramic composition and semiconductor ceramic capacitor
WO1993009071A1 (en) * 1991-10-31 1993-05-13 Motorola, Inc. Method of manufacturing dielectric block filters
US5279850A (en) * 1992-07-15 1994-01-18 Harris Corporation Gas phase chemical reduction of metallic branding layer of electronic circuit package for deposition of branding ink
US5424246A (en) * 1992-07-31 1995-06-13 Kabushiki Kaisha Toshiba Method of manufacturing semiconductor metal wiring layer by reduction of metal oxide
US5561082A (en) * 1992-07-31 1996-10-01 Kabushiki Kaisha Toshiba Method for forming an electrode and/or wiring layer by reducing copper oxide or silver oxide
US5728626A (en) * 1993-07-26 1998-03-17 At&T Global Information Solutions Company Spin-on conductor process for integrated circuits
US6010749A (en) * 1998-10-28 2000-01-04 Goldman; Mark A. Process for the production of volatile metal
US6118649A (en) * 1997-01-29 2000-09-12 Murata Manufacturing Co., Ltd. Dielectric paste and thick film capacitor using the same
US6507477B1 (en) 2000-09-11 2003-01-14 John E. Stauffer Electrical capacitor
US20050207094A1 (en) * 2004-03-16 2005-09-22 Borland William J Thick-film dielectric and conductive compositions
EP1578179A3 (en) * 2004-03-16 2006-05-03 E.I. du Pont de Nemours and Company Thick-film dielectric and conductive compositions
US20060282999A1 (en) * 2005-06-20 2006-12-21 Diptarka Majumdar Electrodes, inner layers, capacitors and printed wiring boards and methods of making thereof - part II
US20070138633A1 (en) * 2005-12-21 2007-06-21 Amey Daniel I Jr Thick film capacitors on ceramic interconnect substrates
US20080146028A1 (en) * 2006-12-19 2008-06-19 Wen Yu Method of depositing copper using physical vapor deposition
US20140141175A1 (en) * 2010-09-09 2014-05-22 Aps Materials, Inc. Vibration damping coating
RU2654963C1 (ru) * 2017-03-06 2018-05-23 Акционерное общество "Научно-производственное предприятие "Исток" имени А.И. Шокина" (АО "НПП "Исток" им. Шокина") Способ металлизации диэлектрического материала компонента электронной техники СВЧ
US20190355520A1 (en) * 2018-05-18 2019-11-21 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor and method of manufacturing the same
US20190371526A1 (en) * 2018-06-01 2019-12-05 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor
US11011312B2 (en) 2018-06-12 2021-05-18 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor using molybdenum (Mo) ground layer and manufacturing method of the same
US20220332958A1 (en) * 2019-09-27 2022-10-20 Material Concept, Inc. Copper oxide paste and method for producing electronic parts
US20230092683A1 (en) * 2021-09-10 2023-03-23 Utility Global, Inc. Method of making an electrode

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JPS61183806A (ja) * 1985-02-08 1986-08-16 松下電器産業株式会社 メタライズ組成物
JPS61183807A (ja) * 1985-02-08 1986-08-16 松下電器産業株式会社 メタライズ組成物
JPS61290601A (ja) * 1985-06-19 1986-12-20 松下電器産業株式会社 メタライズ組成物
US4713300A (en) * 1985-12-13 1987-12-15 Minnesota Mining And Manufacturing Company Graded refractory cermet article
US4885038A (en) * 1986-05-01 1989-12-05 International Business Machines Corporation Method of making multilayered ceramic structures having an internal distribution of copper-based conductors
JPS6355807A (ja) * 1986-08-27 1988-03-10 古河電気工業株式会社 導電性ペ−スト
JP2788510B2 (ja) * 1989-10-27 1998-08-20 第一工業製薬株式会社 銅ペースト組成物
FR2660320A1 (fr) * 1990-04-03 1991-10-04 Europ Composants Electron Encre de terminaison pour composants ceramiques, procede de preparation d'une telle encre et son utilisation dans un condensateur electrique.

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Marion, R. H. et al., Non Noble Termination Method for Chip Capacitors, The International Journal for Hybrid Microelectronics, vol. 5, No. 2, 1982, pp. 50 53. *

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US5279850A (en) * 1992-07-15 1994-01-18 Harris Corporation Gas phase chemical reduction of metallic branding layer of electronic circuit package for deposition of branding ink
US5561082A (en) * 1992-07-31 1996-10-01 Kabushiki Kaisha Toshiba Method for forming an electrode and/or wiring layer by reducing copper oxide or silver oxide
US5424246A (en) * 1992-07-31 1995-06-13 Kabushiki Kaisha Toshiba Method of manufacturing semiconductor metal wiring layer by reduction of metal oxide
US5728626A (en) * 1993-07-26 1998-03-17 At&T Global Information Solutions Company Spin-on conductor process for integrated circuits
US6118649A (en) * 1997-01-29 2000-09-12 Murata Manufacturing Co., Ltd. Dielectric paste and thick film capacitor using the same
US6010749A (en) * 1998-10-28 2000-01-04 Goldman; Mark A. Process for the production of volatile metal
US6507477B1 (en) 2000-09-11 2003-01-14 John E. Stauffer Electrical capacitor
US7688569B2 (en) 2004-03-16 2010-03-30 E. I. Du Pont De Nemours And Company Thick-film dielectric and conductive compositions
US20050207094A1 (en) * 2004-03-16 2005-09-22 Borland William J Thick-film dielectric and conductive compositions
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US20060282999A1 (en) * 2005-06-20 2006-12-21 Diptarka Majumdar Electrodes, inner layers, capacitors and printed wiring boards and methods of making thereof - part II
US20070138633A1 (en) * 2005-12-21 2007-06-21 Amey Daniel I Jr Thick film capacitors on ceramic interconnect substrates
US7531416B2 (en) 2005-12-21 2009-05-12 E. I. Du Pont De Nemours And Company Thick film capacitors on ceramic interconnect substrates
US20080146028A1 (en) * 2006-12-19 2008-06-19 Wen Yu Method of depositing copper using physical vapor deposition
US8791018B2 (en) * 2006-12-19 2014-07-29 Spansion Llc Method of depositing copper using physical vapor deposition
US9728414B2 (en) 2006-12-19 2017-08-08 Cypress Semiconductor Corporation Method of depositing copper using physical vapor deposition
US20140141175A1 (en) * 2010-09-09 2014-05-22 Aps Materials, Inc. Vibration damping coating
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US20190355520A1 (en) * 2018-05-18 2019-11-21 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor and method of manufacturing the same
US11081282B2 (en) * 2018-05-18 2021-08-03 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor with copper oxide layer and method of manufacturing the same
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US11705281B2 (en) * 2018-05-18 2023-07-18 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor and method of manufacturing the same
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US20220332958A1 (en) * 2019-09-27 2022-10-20 Material Concept, Inc. Copper oxide paste and method for producing electronic parts
US20230092683A1 (en) * 2021-09-10 2023-03-23 Utility Global, Inc. Method of making an electrode

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EP0125730A1 (en) 1984-11-21
EP0125730B1 (en) 1988-12-28
DE3475799D1 (en) 1989-02-02
JPS59226178A (ja) 1984-12-19
JPH0340109B2 (enrdf_load_html_response) 1991-06-17
HK65990A (en) 1990-08-31

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